Nonaqueous electrolytic solution for lithium secondary battery and lithium secondary battery using the same

ABSTRACT

A non-aqueous electrolytic solution is advantageously used in preparation of a lithium secondary battery excellent in cycle characteristics. In the non-aqueous electrolytic solution for a lithium secondary battery, an electrolyte salt is dissolved in a non-aqueous solvent. The non-aqueous electrolytic solution further contains a vinylene carbonate compound in an amount of 0.01 to 10 wt. %, and an alkyne compound in an amount of 0.01 to 10 wt. %.

FIELD OF THE INVENTION

The present invention relates to a lithium secondary battery showing excellent cycle characteristics, and a non-aqueous electrolytic solution advantageously used in preparation of the lithium secondary battery excellent in cycle characteristics.

BACKGROUND OF THE INVENTION

The lithium secondary battery has recently been widely used for example, as an electric source for driving small-sized electronics. The lithium secondary battery has a basic structure comprising a positive electrode, a negative electrode and a non-aqueous electrolytic solution, which are contained in a sealed cell. The positive electrode preferably comprises a complex oxide of lithium such as LiCoO₂, and the negative electrode preferably comprises a carbon material or metallic lithium. A carbonate such as ethylene carbonate (EC) or propylene carbonate (PC) has been advantageously used in the non-aqueous electrolytic solution for the lithium secondary battery.

The recent lithium secondary battery requires a further improvement on battery performance such as cycle characteristics of the battery and electric capacity.

In a lithium secondary battery, a complex oxide of lithium such as LiCoO₂, LiMn₂O₄ and LiNiO₂ is often used as a positive electrode material. A process of recharging the battery causes a local oxidation and decomposition reaction of a part of a solvent contained in a non-aqueous electrolytic solution. A decomposition product inhibits an ordinary electrochemical reaction of the battery to lower battery performance. The reason is considered that a solvent is electrochemically oxidized along an interface between the positive electrode material and the non-aqueous electrolytic solution.

In a lithium secondary battery, a highly crystallized carbon material such as natural or artificial graphite is often used as a negative electrode material. A process of recharging the battery causes a local reduction and decomposition reaction of a part of a solvent contained in a non-aqueous electrolytic solution. Ethylene carbonate (EC) is widely used as a solvent of the non-aqueous electrolytic solvent. Ethylene carbonate may particularly be reduced and decomposed to lower battery performance while repeating charge and discharge.

Japanese Patent Provisional Publication No. 8(1996)-45545 and U.S. Pat. No. 5,626,981 recommend adding a vinylene carbonate compound to a non-aqueous electrolytic solution to improve battery performance of the lithium secondary battery. It is further reported that the cycle life is lengthened using the electric solution containing the vinylene carbonate compound.

Japanese Patent Provisional Publication Nos. 2000-195545, 2001-313072, 2002-100399 and 2002-124297 and U.S. Pat. No. 6,479,191 B1 recommend adding an alkyne compound to a non-aqueous electrolytic solution to improve battery performance of the lithium secondary battery. It is further reported that the cycle life is lengthened using the electric solution containing the alkyne compound.

Increase in density of a positive electrode composition layer or a negative electrode composition layer has recently been examined to enlarge capacity of the lithium secondary battery. Japanese Patent Provisional Publication No. 2003-142075 describes a lithium secondary battery comprising a positive electrode composition layer having a density of 3.3 to 3.7 g/cm³ provided on aluminum foil, and a negative electrode composition layer having a density of 1.4 to 1.8 g/cm³ provided on copper foil. It is further reported that the obtained lithium secondary battery has high energy density and high safety, and can be preserved at an elevated temperature.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

As is described in the above-mentioned documents, battery performance such as cycle characteristics can be improved by adding a vinylene carbonate compound or an alkyne compound to a non-aqueous electrolytic solution of a lithium secondary battery.

The conventional lithium secondary battery comprises positive electrode and negative electrode composition layers of relatively low density. The battery performance such as the cycle characteristics can be improved by adding a vinylene carbonate compound or an alkyne compound to a non-aqueous electrolytic solution of the conventional lithium secondary battery.

On the other hand, the recent lithium secondary battery comprises positive electrode and negative electrode composition layers of high density. The present inventors have found that cycle characteristics are scarcely improved by adding the above-mentioned additive to the non-aqueous electrolytic solution of the recent lithium secondary battery. The inventors have further found that the electrolytic solution is decomposed in the battery to cause shortage (dry up) of the electrolytic solution. The cycle characteristics mean a feature of keeping a high charge capacity after repeating charge and discharge operations many times.

An object of the present invention is to provide a non-aqueous electrolytic solution that has solved the above-mentioned problems of the non-aqueous electrolytic solution for the lithium secondary battery.

MEANS TO SOLVE THE PROBLEM

The present invention provides a non-aqueous electrolytic solution for a lithium secondary battery in which an electrolyte salt is dissolved in a non-aqueous solvent, wherein the non-aqueous electrolytic solution further contains a vinylene carbonate compound represented by the formula (I) in an amount of 0.01 to 10 wt. %, and an alkyne compound represented by the formula (II), (III), (IV), (V), (VI) or (VII) in an amount of 0.01 to 10 wt. %:

(in which each of R¹ and R² independently is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

(in which each of R³ to R⁵ independently is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, or R⁴ and R⁵ are combined with each other to form a cycloalkylene group having 3 to 6 carbon atoms; x is 1 or 2; and Y¹ is —COOR²⁰, —COR²⁰ or —SO₂R²⁰, wherein R²⁰ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms)

(in which each of R⁶ to R⁹ independently is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, or R⁶ and R⁷ or R⁸ and R⁹ are combined with each other to form a cycloalkylene group having 3 to 6 carbon atoms; x is 1 or 2; Y² is —COOR²¹, —COR²¹ or —SO₂R²¹, wherein R²¹ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms; and Y³ is —COOR²², —COR²² or —SO₂R²², wherein R²² is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms)

(in which each of R¹⁰ to R¹³ independently is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, or R¹⁰ and R¹¹ or R¹² and R¹³ are combined with each other to form a cycloalkylene group having 3 to 6 carbon atoms; x is 1 or 2; Y⁴ is —COOR²³, —COR²³ or —SO₂R²³, wherein R²³ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms; and Y⁵ is —COOR²⁴, —COR²⁴ or —SO₂R²⁴, wherein R²⁴ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms)

(in which each of R¹⁴ to R¹⁹ independently is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, or R¹⁵ and R¹⁶ or R¹⁷ and R¹⁸ are combined with each other to form a cycloalkylene group having 3 to 6 carbon atoms; and x is 1 or 2)

(in which each of R²⁵ to R²⁷ independently is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, or R²⁶ and R²⁷ are combined with each other to form a cycloalkylene group having 3 to 6 carbon atoms; x is 1 or 2; W is sulfinyl, sulfonyl or oxalyl; and Y⁶ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms)

(in which R²⁸ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms; R²⁹ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms; and p is 1 or 2).

The non-aqueous electrolytic solution according to the present invention contains both a specific amount of a vinylene carbonate compound and a specific amount of an alkyne compound. The non-aqueous electrolytic solution can be advantageously used in a lithium secondary battery of high capacity comprising a positive electrode and negative electrode composition layers of high density. The lithium secondary battery comprising the non-aqueous electrolytic solution according to the present invention is improved in cycle characteristics without causing phenomenon of dry up. The function and effect have not yet clarified, but are considered to be obtained by a strong film formed on a negative electrode using both the vinylene carbonate compound and the alkyne compound. The improvement on the cycle characteristics is obtained using the non-aqueous electrolytic solution according to the present invention. The improvement is also effective in a conventional lithium secondary battery comprising positive electrode and negative electrode layers of relatively low density.

EFFECT OF THE INVENTION

The cycle characteristics of the lithium secondary battery are improved by using the non-aqueous electrolytic solution according to the present invention. The non-aqueous electrolytic solution according to the present invention is particularly effective in improving cycle characteristics of a lithium secondary battery (of high charge capacity) comprising positive electrode or negative electrode composition layer of high density.

BEST MODE FOR CARRYING OUT THE INVENTION

In the vinylene carbonate compound according to the present invention represented by the formula (I), each of R¹ and R² independently is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl and butyl. R¹ and R² can be identical, for example, both can be methyl or both can be ethyl. R¹ and R² can be different from each other, for example, they can be a combination of methyl and ethyl.

Examples of the vinylene carbonate compound represented by the formula (I) include vinylene carbonate, 4-methyl-1,3-dioxolen-2-one, 4-ethyl-1,3-dioxolen-2-one, 4-propyl-1,3-dioxolen-2-one, 4-butyl-1,3-dioxolen-2-one, 4-tert-butyl-1,3-dioxolen-2-one, 4,5-dimethyl-1,3-dioxolen-2-one, 4,5-diethyl-1,3-dioxolen-2-one, 4,5-dipropyl-1,3-dioxolen-2-one, 4,5-dibutyl-1,3-dioxolen-2-one, 4,5-ditert-butyl-1,3-dioxolen-2-one, 4-ethyl-5-methyl-1,3-dioxolen-2-one, 4-methyl-5-butyl-1,3-dioxolen-2-one and 4-methyl-5-tert-butyl-1,3-dioxolen-2-one. Vinylene carbonate is particularly preferred.

An excess amount of the vinylene carbonate compound represented by the formula (I) contained in the nonaqueous electrolytic solution might lower battery performance. On the other hand, shortage of the vinylene carbonate might cause insufficient battery performance. The non-aqueous electrolytic solution contains the vinylene carbonate compound preferably in an amount of 0.01 wt. % or more, more preferably in an amount of 0.05 wt. % or more, and most preferably in an amount of 0.1 wt. % or more. Further, the non-aqueous electrolytic solution contains the vinylene carbonate compound preferably in an amount of 10 wt. % or less, more preferably in an amount of 5 wt. % or less, and most preferably in an amount of 3 wt. % or less. Accordingly, the non-aqueous electrolytic solution contains the vinylene carbonate compound preferably in an amount of 0.01 to 10 wt. %, more preferably in an amount of 0.05 to 5 wt. %, and most preferably in an amount of 0.1 to 3 wt. %.

An alkyne compound is used in combination with the vinylene carbonate compound in the present invention. The alkyne compound is described below.

Examples of the alkyne compound represented by the formula (II) are shown below.

(1) Y¹ is —COOR²⁰

2-Propynyl methyl carbonate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is methyl, and x is 1)

1-Methyl-2-propynyl methyl carbonate (R³ is hydrogen, R⁴ is methyl, R⁵ is hydrogen, R²⁰ is methyl, and x is 1)

2-Propynyl ethyl carbonate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is ethyl, and x is 1)

2-Propynyl propyl carbonate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is propyl, and x is 1)

2-Propynyl butyl carbonate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is butyl, and x is 1)

2-Propynyl phenyl carbonate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is phenyl, and x is 1)

2-Propynyl cyclohexyl carbonate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is cyclohexyl, and x is 1)

2-Butynyl methyl carbonate (R³ is methyl, each of R⁴ and R⁵ is hydrogen, R²⁰ is methyl, and x is 1)

3-Butynyl methyl carbonate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is methyl, and x is 2)

2-Pentynyl methyl carbonate (R³ is ethyl, each of R⁴ and R⁵ is hydrogen, R²⁰ is methyl, and x is 1)

1-Methyl-2-butynyl methyl carbonate (each of R³ and R⁴ is methyl, R⁵ is hydrogen, R²⁰ is methyl, and x is 1)

1,1-Dimethyl-2-propynyl methyl carbonate (R³ is hydrogen, each of R⁴ and R⁵ is methyl, R²⁰ is methyl, and x is 1)

1,1-Diethyl-2-propynyl methyl carbonate (R³ is hydrogen, each of R⁴ and R⁵ is ethyl, R²⁰ is methyl, and x is 1)

1-Ethyl-1-methyl-2-propynyl methyl carbonate (R³ is hydrogen, R⁴ is ethyl, R⁵ is methyl, R²⁰ is methyl, and x is 1)

1-Isobutyl-1-methyl-2-propynyl methyl carbonate (R³ is hydrogen, R⁴ is isobutyl, R⁵ is methyl, R²⁰ is methyl, and x is 1)

1,1-Dimethyl-2-butynyl methyl carbonate (each of R³, R⁴ and R⁵ is methyl, R²⁰ is methyl, and x is 1)

1-Ethynylcyclohexyl methyl carbonate (R³ is hydrogen, combination of R⁴ and R⁵ is pentamethylene, R²⁰ is methyl, and x is 1)

1-Methyl-1-phenyl-2-propynyl methyl carbonate (R³ is hydrogen, R⁴ is phenyl, R⁵ is methyl, R²⁰ is methyl, and x is 1)

1,1-Diphenyl-2-propynyl methyl carbonate (R³ is hydrogen, each of R⁴ and R⁵ is phenyl, R²⁰ is methyl, and x is 1)

1,1-Dimethyl-2-propynyl ethyl carbonate (R³ is hydrogen, each of R⁴ and R⁵ is methyl, R²⁰ is ethyl, and x is 1)

(2) Y¹ is —COR²⁰

2-Propynyl formate (each of R³, R⁴, R⁵ and R²⁰ is hydrogen, and x is 1)

1-Methyl-2-propynyl formate (R³ is hydrogen, R⁴ is methyl, R⁵ is hydrogen, R²⁰ is hydrogen, and x is 1)

2-Propynyl acetate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is methyl, and x is 1)

1-Methyl-2-propynyl acetate (R³ is hydrogen, R⁴ is methyl, R⁵ is hydrogen, R²⁰ is methyl, and x is 1)

2-Propynyl propionate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is ethyl, and x is 1)

2-Propynyl butyrate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is propyl, and x is 1)

2-Propynyl benzoate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is phenyl, and x is 1)

2-Propynyl cyclohexanecarboxylate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is cyclohexyl, and x is 1)

2-Butynyl formate (R³ is methyl, each of R⁴, R⁵ and R²⁰ is hydrogen, and x is 1)

3-Butynyl formate (each of R³, R⁴, R⁵ and R²⁰ is hydrogen, and x is 2)

2-Pentynyl formate (R³ is ethyl, each of R⁴, R⁵ and R²⁰ is hydrogen, and x is 1)

1-Methyl-2-butynyl formate (each of R³ and R⁴ is methyl, each of R⁵ and R²⁰ is hydrogen, and x is 1)

1,1-Dimethyl-2-propynyl formate (R³ is hydrogen, each of R⁴ and R⁵ is methyl, R²⁰ is hydrogen, and x is 1)

1,1-Diethyl-2-propynyl formate (R³ is hydrogen, each of R⁴ and R⁵ is ethyl, R²⁰ is hydrogen, and x is 1)

1-Ethyl-1-methyl-2-propynyl formate (R³ is hydrogen, R⁴ is ethyl, R⁵ is methyl, R²⁰ is hydrogen, and x is 1)

1-Isobutyl-1-methyl-2-propynyl formate (R³ is hydrogen, R⁴ is isobutyl, R⁵ is methyl, R²⁰ is hydrogen, and x is 1)

1,1-Dimethyl-2-butynyl formate (each of R³, R⁴ and R⁵ is methyl, R²⁰ is hydrogen, and x is 1)

1-Ethynylcyclohexyl formate (R³ is hydrogen, combination of R⁴ and R⁵ is pentamethylene, R²⁰ is hydrogen, and x is 1)

1-Methyl-1-phenyl-2-propynyl formate (R³ is hydrogen, R⁴ is phenyl, R⁵ is methyl, R²⁰ is hydrogen, and x is 1)

1,1-Diphenyl-2-propynyl formate (R³ is hydrogen, each of R⁴ and R⁵ is phenyl, R²⁰ is hydrogen, and x is 1)

2-Butynyl acetate (R³ is methyl, each of R⁴ and R⁵ is hydrogen, R²⁰ is methyl, and x is 1)

3-Butynyl acetate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is methyl, and x is 2)

2-Pentynyl acetate (R³ is ethyl, each of R⁴ and R⁵ is hydrogen, R²⁰ is methyl, and x is 1)

1-Methyl-2-butynyl acetate (each of R³ and R⁴ is methyl, R⁵ is hydrogen, R²⁰ is methyl, and x is 1)

1,1-Dimethyl-2-propynyl acetate (R³ is hydrogen, each of R⁴ and R⁵ is methyl, R²⁰ is methyl, and x is 1)

1,1-Diethyl-2-propynyl acetate (R³ is hydrogen, each of R⁴ and R⁵ is ethyl, R²⁰ is methyl, and x is 1)

1-Ethyl-1-methyl-2-propynyl acetate (R³ is hydrogen, R⁴ is ethyl, R⁵ is methyl, R²⁰ is methyl, and x is 1)

1-Isobutyl-1-methyl-2-propynyl acetate (R³ is hydrogen, R⁴ is isobutyl, R⁵ is methyl, R²⁰ is methyl, and x is 1)

1,1-Dimethyl-2-butynyl acetate (each of R³, R⁴ and R⁵ is methyl, R²⁰ is methyl, and x is 1)

1-Ethynylcyclohexyl acetate (R³ is hydrogen, combination of R⁴ and R⁵ is pentamethylene, R²⁰ is methyl, and x is 1)

1-Methyl-1-phenyl-2-propynyl acetate (R³ is hydrogen, R⁴ is phenyl, R⁵ is methyl, R²⁰ is methyl, and x is 1)

1,1-Diphenyl-2-propynyl acetate (R³ is hydrogen, each of R⁴ and R⁵ is phenyl, R²⁰ is methyl, and x is 1)

1,1-Dimethyl-2-propynyl propionate (R³ is hydrogen, each of R⁴ and R⁵ is methyl, R²⁰ is ethyl, and x is 1)

(3) Y¹ is —SO₂R²⁰

2-Propynyl methanesulfonate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is methyl, and x is 1)

1-Methyl-2-propynyl methanesulfonate (R³ is hydrogen, R⁴ is methyl, R⁵ is hydrogen, R²⁰ is methyl, and x is 1)

2-Propynyl ethanesulfonate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is ethyl, and x is 1)

2-Propynyl propanesulfonate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is propyl, and x is 1)

2-Propynyl p-toluenesulfonate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is p-tolyl, and x is 1)

2-Propynyl cyclohexanesulfonate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is cyclohexyl, and x is 1)

2-Butynyl methanesulfonate (R³ is methyl, each of R⁴ and R⁵ is hydrogen, R²⁰ is methyl, and x is 1)

3-Butynyl methanesulfonate (each of R³, R⁴ and R⁵ is hydrogen, R²⁰ is methyl, and x is 2)

2-Pentynyl methanesulfonate (R³ is ethyl, each of R⁴ and R⁵ is hydrogen, R²⁰ is methyl, and x is 1)

1-Methyl-2-butynyl methanesulfonate (each of R³ and R⁴ is methyl, R⁵ is hydrogen, R²⁰ is methyl, and x is 1)

1,1-Dimethyl-2-propynyl methanesulfonate (R³ is hydrogen, each of R⁴ and R⁵ is methyl, R²⁰ is methyl, and x is 1)

1,1-Diethyl-2-propynyl methanesulfonate (R³ is hydrogen, each of R⁴ and R⁵ is ethyl, R²⁰ is methyl, and x is 1)

1-Ethyl-1-methyl-2-propynyl methanesulfonate (R³ is hydrogen, R⁴ is ethyl, R⁵ is methyl, R²⁰ is methyl, and x is 1)

1-Isobutyl-1-methyl-2-propynyl methanesulfonate (R³ is hydrogen, R⁴ is isobutyl, R⁵ is methyl, R²⁰ is methyl, and x is 1)

1,1-Dimethyl-2-butynyl methanesulfonate (each of R³, R⁴ and R⁵ is methyl, R²⁰ is methyl, and x is 1)

1-Ethynylcyclohexyl methanesulfonate (R³ is hydrogen, combination of R⁴ and R⁵ is pentamethylene, R²⁰ is methyl, and x is 1)

1-Methyl-1-phenyl-2-propynyl methanesulfonate (R³ is hydrogen, R⁴ is phenyl, R⁵ is methyl, R²⁰ is methyl, and x is 1)

1,1-Diphenyl-2-propynyl methanesulfonate (R³ is hydrogen, each of R⁴ and R⁵ is phenyl, R²⁰ is methyl, and x is 1)

1,1-Dimethyl-2-propynyl ethanesulfonate (R³ is hydrogen, each of R⁴ and R⁵ is methyl, R²⁰ is ethyl, and x is 1)

Examples of the alkyne compound represented by the formula (III) are shown below.

(1) Y² is —COOR²¹ and Y³ is —COOR²²

2-Butynylene bis(methyl carbonate) (each of R⁶, R⁷, R⁸ and R⁹ is hydrogen, each of R²¹ and R²² is methyl, and x is 1)

2-Butynylene bis(ethyl carbonate) (each of R⁶, R⁷, R⁸ and R⁹ is hydrogen, each of R²¹ and R²² is ethyl, and x is 1)

1,4-Dimethyl-2-butynylene bis(methyl carbonate) (each of R⁶ and R⁸ is methyl, each of R⁷ and R⁹ is hydrogen, each of R²¹ and R²² is methyl, and x is 1)

1,4-Dimethyl-2-butynylene bis(ethyl carbonate) (each of R⁶ and R⁸ is methyl, each of R⁷ and R⁹ is hydrogen, each of R²¹ and R²² is ethyl, and x is 1)

1,1,4,4-Tetramethyl-2-butynylene bis(methyl carbonate) (each of R⁶, R⁷, R⁸ and R⁹ is methyl, each of R²¹ and R²² is methyl, and x is 1)

1,1,4,4-Tetramethyl-2-butynylene bis(ethyl carbonate) (each of R⁶, R⁷, R⁸ and R⁹ is methyl, each of R²¹ and R²² is ethyl, and x is 1)

(2) Y² is —COR²¹ and Y³ is —COR²²

2-Butynylene diformate (each of R⁶, R⁷, R⁸, R⁹, R²¹ and R²² is hydrogen, and x is 1)

2-Butynylene diacetate (each of R⁶, R⁷, R⁸ and R⁹ is hydrogen, each of R²¹ and R²² is methyl, and x is 1)

2-Butynylene dipropionate (each of R⁶, R⁷, R⁸ and R⁹ is hydrogen, each of R²¹ and R²² is ethyl, and x is 1)

1,4-Dimethyl-2-butynylene diformate (each of R⁶ and R⁸ is methyl, each of R⁷, R⁹, R²¹ and R²² is hydrogen, and x is 1)

1,4-Dimethyl-2-butynylene diacetate (each of R⁶ and R⁸ is methyl, each of R⁷ and R⁹ is hydrogen, each of R²¹ and R²² is methyl, and x is 1)

1,4-Dimethyl-2-butynylene dipropionate (each of R⁶ and R⁸ is methyl, each of R⁷ and R⁹ is hydrogen, each of R²¹ and R²² is ethyl, and x is 1)

1,1,4,4-Tetramethyl-2-butynylene diformate (each of R⁶, R⁷, R⁸ and R⁹ is methyl, each of R²¹ and R²² is hydrogen, and x is 1)

1,1,4,4-Tetramethyl-2-butynylene diacetate (each of R⁶, R⁷, R⁸ and R⁹ is methyl, each of R²¹ and R²² is methyl, and x is 1)

1,1,4,4-Tetramethyl-2-butynylene dipropionate (each of R⁶, R⁷, R⁸ and R⁹ is methyl, each of R²¹ and R²² is ethyl, and x is 1)

(3) Y² is —SO₂R²¹ and Y³ is —SO₂R²²

2-Butynylene bis(methanesulfonate) (each of R⁶, R⁷, R⁸ and R⁹ is hydrogen, each of R²¹ and R²² is methyl, and x is 1)

2-Butynylene bis(ethanesulfonate) (each of R⁶, R⁷, R⁸ and R⁹ is hydrogen, each of R²¹ and R²² is ethyl, and x is 1)

1,4-Dimethyl-2-butynylene bis(methanesulfonate) (each of R⁶ and R⁸ is methyl, each of R⁷ and R⁹ is hydrogen, each of R²¹ and R²² is methyl, and x is 1)

1,4-Dimethyl-2-butynylene bis(ethanesulfonate) (each of R⁶ and R⁸ is methyl, each of R⁷ and R⁹ is hydrogen, each of R²¹ and R²² is ethyl, and x is 1)

1,1,4,4-Tetramethyl-2-butynylene bis(methanesulfonate) (each of R⁶, R⁷, R⁸ and R⁹ is methyl, each of R²¹ and R²² is methyl, and x is 1)

1,1,4,4-Tetramethyl-2-butynylene bis(ethanesulfonate) (each of R⁶, R⁷, R⁸ and R⁹ is methyl, each of R²¹ and R²² is ethyl, and x is 1)

Examples of the alkyne compound represented by the formula (IV) are shown below.

(1) Y⁴ is —COOR²³ and Y⁵ is —COOR²⁴

2,4-Hexadiynylene bis(methyl carbonate) (each of R¹⁰, R¹¹, R¹² and R¹³ is hydrogen, each of R²³ and R²⁴ is methyl, and x is 1)

2,4-Hexadiynylene bis(ethyl carbonate) (each of R¹⁰, R¹¹, R¹² and R¹³ is hydrogen, each of R²³ and R²⁴ is ethyl, and x is 1)

1,1,6,6-Tetramethyl-2,4-hexadiynylene bis(methyl carbonate) (each of R¹⁰, R¹¹, R¹² and R¹³ is methyl, each of R²³ and R²⁴ is methyl, and x is 1)

1,1,6,6-Tetramethyl-2,4-hexadiynylene bis(ethyl carbonate) (each of R¹⁰, R¹¹, R¹² and R¹³ is methyl, each of R²³ and R²⁴ is ethyl, and x is 1)

(2) Y⁴ is —COR²³ and Y⁵ is —COR²⁴

2,4-Hexadiynylene diformate (each of R¹⁰, R¹¹, R¹², R¹³, R²³ and R²⁴ is hydrogen, and x is 1)

2,4-Hexadiynylene diacetate (each of R¹⁰, R¹¹, R¹² and R¹³ is hydrogen, each of R²³ and R²⁴ is methyl, and x is 1)

2,4-Hexadiynylene dipropionate (each of R¹⁰, R¹¹, R¹² and R¹³ is hydrogen, each of R²³ and R²⁴ is ethyl, and x is 1)

1,1,6,6-Tetramethyl-2,4-hexadiynylene diformate (each of R¹⁰, R¹¹, R¹² and R¹³ is methyl, each of R²³ and R²⁴ is hydrogen, and x is 1)

1,1,6,6-Tetramethyl-2,4-hexadiynylene diacetate (each of R¹⁰, R¹¹, R¹² and R¹³ is methyl, each of R²³ and R²⁴ is methyl, and x is 1)

1,1,6,6-Tetramethyl-2,4-hexadiynylene dipropionate (each of R¹⁰, R¹¹, R¹² and R¹³ is methyl, each of R²³ and R²⁴ is ethyl, and x is 1)

(3) Y⁴ is —SO₂R²³ and Y⁵ is —SO₂R²⁴

2,4-Hexadiynylene bis(methanesulfonate) (each of R¹⁰, R¹¹, R¹² and R¹³ is hydrogen, each of R²³ and R²⁴ is methyl, and x is 1)

2,4-Hexadiynylene bis(ethanesulfonate) (each of R¹⁰, R¹¹, R¹² and R¹³ is hydrogen, each of R²³ and R²⁴ is ethyl, and x is 1)

1,1,6,6-Tetramethyl-2,4-hexadiynylene bis(methanesulfonate) (each of R¹⁰, R¹¹, R¹² and R¹³ is methyl, each of R²³ and R²⁴ is methyl, and x is 1)

1,1,6,6-Tetramethyl-2,4-hexadiynylene bis(ethanesulfonate) (each of R¹⁰, R¹¹, R¹² and R¹³ is methyl, each of R²³ and R²⁴ is ethyl, and x is 1)

Examples of the alkyne compound represented by the formula (V) are shown below.

Di(2-propynyl) carbonate (each of R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ is hydrogen, and x is 1)

Bis(1-methyl-2-propynyl) carbonate (each of R¹⁴, R¹⁶, R¹⁸ and R¹⁹ is hydrogen, each of R¹⁵ and R¹⁷ is methyl, and x is 1)

Di(2-butynyl) carbonate (each of R¹⁴ and R¹⁹ is methyl, each of R¹⁵, R¹⁶, R¹⁷ and R¹⁸ is hydrogen, and x is 1)

Di(3-butynyl) carbonate (each of R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ is hydrogen, and x is 2)

Di(2-pentynyl) carbonate (each of R¹⁴ and R¹⁹ is ethyl, each of R¹⁵, R¹⁶, R¹⁷ and R¹⁸ is hydrogen, and x is 1)

Bis(1-methyl-2-butynyl) carbonate (each of R¹⁴, R¹⁵, R¹⁶ and R¹⁹ is methyl, each of R¹⁷ and R¹⁸ is hydrogen, and x is 1)

2-Propynyl 2-butynyl carbonate (each of R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ is hydrogen, R¹⁹ is methyl, and x is 1)

Bis(1,1-dimethyl-2-propynyl) carbonate (each of R¹⁴ and R¹⁹ is hydrogen, each of R¹⁵, R¹⁶; R¹⁷ and R¹⁸ is methyl, and x is 1)

Bis(1,1-diethyl-2-propynyl) carbonate (each of R¹⁴, and R¹⁹ is hydrogen, each of R¹⁵, R¹⁶, R¹⁷ and R¹⁸ is ethyl, and x is 1)

Bis(1-ethyl-1-methyl-2-propynyl) carbonate (each of R¹⁴ and R¹⁹ is hydrogen, each of R¹⁵ and R¹⁷ is ethyl, each of R¹⁶ and R¹⁸ is methyl, and x is 1)

Bis(1-isobutyl-1-methyl-2-propynyl) carbonate (each of R¹⁴ and R¹⁹ is hydrogen, each of R¹⁵ and R¹⁷ is isobutyl, each of R¹⁶ and R¹⁸ is methyl, and x is 1)

Bis(1,1-dimethyl-2-butynyl) carbonate (each of R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸ and R¹⁹ is methyl, and x is 1)

Bis(1-ethynylcyclohexyl) carbonate (each of R¹⁴ and R¹⁹ is hydrogen, combination of R¹⁵ and R¹⁶ is pentamethylene, combination of R¹⁷ and R¹⁸ is pentamethylene, and x is 1).

Examples of the alkyne compound represented by the formula (VI) are shown below.

(1) W is sulfinyl

Di(2-propynyl) sulfite (each of R²⁵, R²⁶ and R²⁷ is hydrogen, Y⁶ is 2-propynyl, and x is 1)

Bis(1-methyl-2-propynyl) sulfite (R²⁵ is hydrogen, R²⁶ is methyl, R²⁷ is hydrogen, Y⁶ is 1-methyl-2-propynyl, and x is 1)

Di(2-butynyl) sulfite (R²⁵ is methyl, each of R²⁶ and R²⁷ is hydrogen, Y⁶ is 2-butynyl, and x is 1)

Di(3-butynyl) sulfite (each of R²⁵, R²⁶ and R²⁷ is hydrogen, Y⁶ is 3-butynyl, and x is 2)

Di(2-pentynyl) sulfite (R²⁵ is ethyl, each of R²⁶ and R²⁷ is hydrogen, Y⁶ is 2-pentynyl, and x is 1)

Bis(1-methyl-2-butynyl) sulfite (each of R²⁵ and R²⁶ is methyl, R²⁷ is hydrogen, Y⁶ is 1-methyl-2-butynyl, and x is 1)

Bis(1,1-dimethyl-2-propynyl) sulfite (R²⁵ is hydrogen, each of R²⁶ and R²⁷ is methyl, Y⁶ is 1,1-dimethyl-2-propynyl, and x is 1)

Bis(1,1-diethyl-2-propynyl) sulfite (R²⁵ is hydrogen, each of R²⁶ and R²⁷ is ethyl, Y⁶ is 1,1-diethyl-2-propynyl, and x is 1)

Bis(1-ethyl-1-methyl-2-propynyl) sulfite (R²⁵ is hydrogen, R²⁶ is ethyl, R²⁷ is methyl, Y⁶ is 1-ethyl-1-methyl-2-propynyl, and x is 1)

Bis(1-isobutyl-1-methyl-2-propynyl) sulfite (R²⁵ is hydrogen, R²⁶ is isobutyl, R²⁷ is methyl, Y⁶ is 1-isobutyl-1-methyl-2-propynyl, and x is 1)

Bis(1,1-dimethyl-2-butynyl) sulfite (each of R²⁵, R²⁶ and R²⁷ is methyl, Y⁶ is 1,1-dimethyl-2-butynyl, and x is 1)

Bis(1-ethynylcyclohexyl) sulfite (R²⁵ is hydrogen, combination of R²⁶ and R²⁷ is pentamethylene, Y⁶ is 1-ethynylcyclohexyl, and x is 1)

Bis(1-methyl-1-phenyl-2-propynyl) sulfite (R²⁵ is hydrogen, R²⁶ is phenyl, R²⁷ is methyl, Y⁶ is 1-methyl-1-phenyl-2-propynyl, and x is 1)

Bis(1,1-diphenyl-2-propynyl) sulfite (R²⁵ is hydrogen, each of R²⁶ and R²⁷ is phenyl, Y⁶ is 1,1-diphenyl-2-propynyl, and x is 1)

Methyl 2-propynyl sulfite (each of R²⁵, R²⁶ and R²⁷ is hydrogen, Y⁶ is methyl, and x is 1)

Methyl 1-methyl-2-propynyl sulfite (R²⁵ is hydrogen, R²⁶ is methyl, R²⁷ is hydrogen, Y⁶ is methyl, and x is 1)

Ethyl 2-propynyl sulfite (each of R²⁵, R²⁶ and R²⁷ is hydrogen, Y⁶ is ethyl, and x is 1)

Phenyl 2-propynyl sulfite (each of R²⁵, R²⁶ and R²⁷ is hydrogen, Y⁶ is phenyl, and x is 1)

Cyclohexyl 2-propynyl sulfite (each of R²⁵, R²⁶ and R²⁷ is hydrogen, Y⁶ is cyclohexyl, and x is 1)

(2) W is sulfonyl

Di(2-propynyl) sulfate (each of R²⁵, R²⁶ and R²⁷ is hydrogen) Y⁶ is 2-propynyl, and x is 1)

Bis(1-methyl-2-propynyl) sulfate (R²⁵ is hydrogen, R²⁶ is methyl, R²⁷ is hydrogen, Y⁶ is 1-methyl-2-propynyl, and x is 1)

Di(2-butynyl) sulfate (R²⁵ is methyl, each of R²⁶ and R²⁷ is hydrogen, Y⁶ is 2-butynyl, and x is 1)

Di(3-butynyl) sulfate (each of R²⁵, R²⁶ and R²⁷ is hydrogen, Y⁶ is 3-butynyl, and x is 2)

Di(2-pentynyl) sulfate (R²⁵ is ethyl, each of R²⁶ and R²⁷ is hydrogen, Y⁶ is 2-pentynyl, and x is 1)

Bis(1-methyl-2-butynyl) sulfate (each of R²⁵ and R²⁶ is methyl, R²⁷ is hydrogen, Y⁶ is 1-methyl-2-butynyl, and x is 1)

Bis(1,1-dimethyl-2-propynyl) sulfate (R²⁵ is hydrogen, each of R²⁶ and R²⁷ is methyl, Y⁶ is 1,1-dimethyl-2-propynyl, and x is 1)

Bis(1,1-diethyl-2-propynyl) sulfate (R²⁵ is hydrogen, each of R²⁶ and R²⁷ is ethyl, Y⁶ is 1,1-diethyl-2-propynyl, and x is 1)

Bis(1-ethyl-1-methyl-2-propynyl) sulfate (R²⁵ is hydrogen, R²⁶ is ethyl, R²⁷ is methyl, Y⁶ is 1-ethyl-1-methyl-2-propynyl, and x is 1)

Bis(1-isobutyl-1-methyl-2-propynyl) sulfate (R²⁵ is hydrogen, R²⁶ is isobutyl, R²⁷ is methyl, Y⁶ is 1-isobutyl-1-methyl-2-propynyl, and x is 1)

Bis(1,1-dimethyl-2-butynyl) sulfate (each of R²⁵, R²⁶ and R²⁷ is methyl, Y⁶ is 1,1-dimethyl-2-butynyl, and x is 1)

Bis(1-ethynylcyclohexyl) sulfate (R²⁵ is hydrogen, combination of R²⁶ and R²⁷ is pentamethylene, Y⁶ is 1-ethynylcyclohexyl, and x is 1)

Bis(1-methyl-1-phenyl-2-propynyl) sulfate (R²⁵ is hydrogen, R²⁶ is phenyl, R²⁷ is methyl, Y⁶ is 1-methyl-1-phenyl-2-propynyl, and x is 1)

Bis(1,1-diphenyl-2-propynyl) sulfate (R²⁵ is hydrogen, each of R²⁶ and R²⁷ is phenyl, Y⁶ is 1,1-diphenyl-2-propynyl, and x is 1)

Methyl 2-propynyl sulfate (each of R²⁵, R²⁶ and R²⁷ is hydrogen, Y⁶ is methyl, and x is 1)

Methyl 1-methyl-2-propynyl sulfate (R²⁵ is hydrogen, R²⁶ is methyl, R²⁷ is hydrogen, Y⁶ is methyl, and x is 1)

Ethyl 2-propynyl sulfate (each of R²⁵, R²⁶ and R²⁷ is hydrogen, Y⁶ is ethyl, and x is 1)

Phenyl 2-propynyl sulfate (each of R²⁵, R²⁶ and R²⁷ is hydrogen, Y⁶ is phenyl, and x is 1)

Cyclohexyl 2-propynyl sulfate (each of R²⁵, R²⁶ and R²⁷ is hydrogen, Y⁶ is cyclohexyl, and x is 1)

(3) W is oxalyl

Di(2-propynyl) oxalate (each of R²⁵, R²⁶ and R²⁷ is hydrogen, Y⁶ is 2-propynyl, and x is 1)

Bis(1-methyl-2-propynyl) oxalate (R²⁵ is hydrogen, R²⁶ is methyl, R²⁷ is hydrogen, Y⁶ is 1-methyl-2-propynyl, and x is 1)

Di(2-butynyl) oxalate (R²⁵ is methyl, each of R²⁶ and R²⁷ is hydrogen, Y⁶, is 2-butynyl, and x is 1)

Di(3-butynyl) oxalate (each of R²⁵, R²⁶ and R²⁷ is hydrogen, Y⁶ is 3-butynyl, and x is 2)

Di(2-pentynyl) oxalate (R²⁵ is ethyl, each of R²⁶ and R²⁷ is hydrogen, Y⁶ is 2-pentynyl, and x is 1)

Bis(1-methyl-2-butynyl) oxalate (each of R²⁵ and R²⁶ is methyl, R²⁷ is hydrogen, Y⁶ is 1-methyl-2-butynyl, and x is 1)

Bis(1,1-dimethyl-2-propynyl) oxalate (R²⁵ is hydrogen, each of R²⁶ and R²⁷ is methyl, Y⁶ is 1,1-dimethyl-2-propynyl, and x is 1)

Bis (1,1-diethyl-2-propynyl) oxalate (R²⁵ is hydrogen, each of R²⁶ and R²⁷ is ethyl, Y⁶ is 1,1-diethyl-2-propynyl, and x is 1)

Bis(1-ethyl-1-methyl-2-propynyl) oxalate (R²⁵ is hydrogen, R²⁶ is ethyl, R²⁷ is methyl, Y⁶ is 1-ethyl-1-methyl-2-propynyl, and x is 1)

Bis(1-isobutyl-1-methyl-2-propynyl) oxalate (R²⁵ is hydrogen, R²⁶ is isobutyl, R²⁷ is methyl, Y⁶ is 1-isobutyl-1-methyl-2-propynyl, and x is 1)

Bis(1,1-dimethyl-2-butynyl) oxalate (each of R²⁵, R²⁶ and R²⁷ is methyl, Y⁶ is 1,1-dimethyl-2-butynyl, and x is 1)

Bis(1-ethynylcyclohexyl) oxalate (R²⁵ is hydrogen, combination of R²⁶ and R²⁷ is pentamethylene, Y⁶ is 1-ethynylcyclohexyl, and x is 1)

Bis(1-methyl-1-phenyl-2-propynyl) oxalate (R²⁵ is hydrogen, R²⁶ is phenyl, R²⁷ is methyl, Y⁶ is 1-methyl-1-phenyl-2-propynyl, and x is 1)

Bis(1,1-diphenyl-2-propynyl) oxalate (R²⁵ is hydrogen, each of R²⁶ and R²⁷ is phenyl, Y⁶ is 1,1-diphenyl-2-propynyl, and x is 1)

Methyl 2-propynyl oxalate (each of R²⁵, R²⁶ and R²⁷ is hydrogen, Y⁶ is methyl, and x is 1)

Methyl 1-methyl-2-propynyl oxalate (R²⁵ is hydrogen, R²⁶ is methyl, R²⁷ is hydrogen, Y⁶ is methyl, and x is 1)

Ethyl 2-propynyl oxalate (each of R²⁵, R²⁶ and R²⁷ is hydrogen, Y⁶ is ethyl, and x is 1)

Phenyl 2-propynyl oxalate (each of R²⁵, R²⁶ and R²⁷ is hydrogen, Y⁶ is phenyl, and x is 1)

Cyclohexyl 2-propynyl oxalate (each of R²⁵, R²⁶ and R²⁷ is hydrogen, Y⁶ is cyclohexyl, and x is 1)

Examples of the alkyne compound represented by the formula (VII) are shown below.

2-Pentyne (R²⁸ is methyl, R²⁹ is ethyl, and p is 1)

1-Hexyne (R²⁸ is butyl, R²⁹ is hydrogen, and p is 1)

2-Hexyne (R²⁸ is propyl, R²⁹ is methyl, and p is 1)

3-Hexyne (each of R²⁸ and R²⁹ is ethyl, and p is 1)

1-Heptyne (R²⁸ is pentyl, R²⁹ is hydrogen, and p is 1)

1-Octyne (R²⁸ is hexyl, R²⁹ is hydrogen, and p is 1)

2-Octyne (R²⁸ is methyl, R²⁹ is pentyl, and p is 1)

4-Octyne (each of R²⁸ and R²⁹ is propyl, and p is 1)

1-Decyne (R²⁸ is octyl, R²⁹ is hydrogen, and p is 1)

1-Dodecyne (R²⁸ is decyl, R²⁹ is hydrogen, and p is 1)

Phenylacetylene (R²⁸ is phenyl, R²⁹ is hydrogen, and p is 1)

1-Phenyl-1-propyne (R²⁸ is phenyl, R²⁹ is methyl, and p is 1)

1-Phenyl-1-butyne (R²⁸ is phenyl, R²⁹ is ethyl, and p is 1)

1-Phenyl-1-pentyne (R²⁸ is phenyl, R²⁹ is propyl, and p is 1)

1-Phenyl-1-hexyne (R²⁸ is phenyl, R²⁹ is butyl, and p is 1)

Diphenylacetylene (each of R²⁸ and R²⁹ is phenyl, and p is 1)

4-Ethynyltoluene (R²⁸ is p-tolyl, R²⁹ is hydrogen, and p is 1)

4-Tert-butylphenylacetylene (R²⁸ is 4-tertbutylphenyl,

R²⁹ is hydrogen, and p is 1)

1-Ethynyl-4-fluorobenzene (R²⁸ is p-fluoro'phenyl, R²⁹ is hydrogen, and p is 1)

1,4-Diethynylbenzene (R²⁸ is p-ethynylphenyl, R²⁹ is hydrogen, and p is 1)

Dicyclohexylacetylene (each of R²⁸ and R²⁹ is cyclohexyl, and p is 1)

1,4-Diphenylbutadiyne (each of R²⁸ and R²⁹ is phenyl, and p is 2)

An excess amount of the alkyne compound contained in the non-aqueous electrolytic solution might change conductivity of the electrolytic solution to lower battery performance. The electrolytic solution contains the alkyne compound preferably in an amount of 10 wt. % or less, more preferably in an amount of 5 wt. % or less, and most preferably in an amount of 3 wt. % or less. On the other hand, it is difficult to form a film from an extremely small amount of the alkyne compound. Therefore, shortage of the alkyne compound might cause insufficient battery performance. The electrolytic solution contains the alkyne compound preferably in an amount of 0.01 wt. % or more, more preferably in an amount of 0.05 wt. % or more, and most preferably in an amount of 0.1 wt. % or more. Accordingly, the non-aqueous electrolytic solution contains the alkyne compound preferably in an amount of 0.01 to 10 wt. %, more preferably in an amount of 0.05 to 5 wt. %, and most preferably in an amount of 0.1 to 3 wt. %.

Examples of the non-aqueous solvent used in the nonaqueous electrolytic solution according to the present invention include: cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylethylene carbonate (VEC); lactones such as γ-butyrolactone (GBL), γ-valerolactone (GVL), α-angelica lactone (AGL); chain carbonates such as dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), diethyl carbonate (DEC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC), methyl butyl carbonate (MBC), dibutyl carbonate (DBC); ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane; nitriles such as acetonitrile, adiponitrile; chain esters such as methyl propionate, methyl pivalate, butyl pivalate, octyl pivalate; amides such as dimethylformamide; phosphoric esters such as trimethyl phosphate, trioctyl phosphate; and compounds having a structure of S═O such as 1,3-propanesultone, 1,4-propanesultone, divinyl sulfone, tetramethylene bis(methanesulfonate), ethylene sulfite, propylene sulfite, ethylene sulfate, propylene sulfate.

Examples of combination of the non-aqueous solvents include various combinations such as a combination of a cyclic carbonate and a chain carbonate, a combination of a cyclic carbonate and a lactone, a combination of a cyclic carbonate, a lactone and a chain ester, a combination of a cyclic carbonate, a chain carbonate and a lactone, a combination of a cyclic carbonate, a chain carbonate and an ether, and a combination of a cyclic carbonate, a chain carbonate and a chain ester. The combination of the cyclic carbonate and the chain carbonate, or the combination of the cyclic carbonate, the lactone and the chain carbonate is preferred. The volume ratio of the cyclic carbonate to the chain carbonate is preferably in the range of 1:9 to 10:0, and more preferably in the range of 2:8 to 7:3.

Examples of the electrolyte salt used in the nonaqueous electrolytic solution include: LiPF₆; LiBF₄; LiClO₄; lithium salts comprising a chain alkyl group such as LiN(SO₂CF₃)₂, LiN(SO₂C₂F₅)₂, LiC(SO₂CF₃)₃, LiPF₄(CF₃)₂, LiPF₃(C₂F₅)₃, LiPF₃(CF₃)₃, LiPF₃(iso-C₃F₇)₃, LiPF₅(iso-C₃F₇); and lithium salts comprising a cyclic alkylene group such as (CF₂)₂(SO₂)₂NLi, (CF₂)₃(SO₂)₂NLi. Only one electrolyte salt can be used in the solution. Further, two or more electrolyte salts can be used in combination. The concentration of the electrolyte salts dissolved in the non-aqueous medium is preferably of 0.3 M or more, more preferably of 0.5 M or more, and most preferably of 0.7 M or more. The concentration is preferably of 3 M or less, more preferably of 2.5 M or less, and most preferably of 2 M or less.

The non-aqueous electrolytic solution according to the present invention can be obtained by mixing nonaqueous solvents such as ethylene carbonate, propylene carbonate, methyl ethyl carbonate, dissolving the abovementioned electrolyte salt in the mixture, and dissolving a vinylene carbonate compound and an alkyne compound in the solution.

The non-aqueous electrolytic solution according to the present invention can contain the air or carbon dioxide to inhibit generation of a gas caused by decomposition of the electrolytic solution and to improve battery performance such as cycle and storage characteristics.

Carbon dioxide or the air can be contained (dissolved) in the non-aqueous electrolytic solution in the present invention according to a method (1) of contacting the non-aqueous electrolytic solution to the air or a gas containing carbon dioxide to introduce the air or the gas into the solution, and then injecting the solution into the battery, or a method of (2) injecting the non-aqueous electrolytic solution into the battery, and then introducing the air or a gas containing carbon dioxide into the battery before or after sealing the battery. The two methods can be used in combination. The amount of the moisture contained in the air or the gas containing carbon dioxide is preferably small as possible. The amount of the moisture is so reduced that the due point of the air or the gas is lower than −40° C., and more preferably lower than −50° C.

The non-aqueous electrolytic solution according to the present invention can further contain an aromatic compound to secure safety of the battery from excessive charge. Examples of the aromatic compound include cyclohexylbenzene, a fluorocyclohexylbenzene compound (e.g., 1-fluoro-2-cyclohexylbenzene, 1-fluoro-3-cyclohexylbenzene, 1-fluoro-4-cyclohexylbenzene), biphenyl, terphenyl(o-,m-,p-), diphenyl ether, 2-fluorophenyl phenyl ether, 4-fluorophenyl phenyl ether, fluorobenzene, difluorobenzene(o-,m-,p-), 2-fluorobiphenyl, 4-fluorobiphenyl, 2,4-difluoroanisole, tert-butylbenzene, 1,3-di-tert-butylbenzene, 1-fluoro-4-tert-butylbenzene, tert-pentylbenzene, 4-tert-butylbiphenyl, tert-pentylbiphenyl, a partially hydrogenated o-terphenyl (such as 1,2-dicyclohexylbenzene, 2-phenylbicyclohexyl, 1,2-diphenylcyclohexane, ocyclohexylbiphenyl), a partially hydrogenated m-terphenyl (examples analogous to the examples of the partially hydrogenated o-terphenyl) and a partially hydrogenated p-terphenyl (examples analogous to the examples of the partially hydrogenated o-terphenyl). The non-aqueous electrolytic solution contains the aromatic compound preferably in an amount of 0.1 to 5 wt. %.

Two or more aromatic compounds can be used in combination. Examples of the combination include biphenyl and cyclohexylbenzene, cyclohexylbenzene and tert-butylbenzene, cyclohexylbenzene and tert-pentylbenzene, biphenyl and fluorobenzene, cyclohexylbenzene and fluorobenzene, 2,4-difluoroanisole and cyclohexylbenzene, cyclohexylbenzene and 1-fluoro-4-tert-butylbenzene, cyclohexylbenzene and a fluorocyclohexylbenzene compound, a fluorocyclohexylbenzene compound and fluorobenzene, and 2,4-difluoroanisole and a fluorocyclohexylbenzene compound. The weight mixing ratio is preferably in the range of 50:50 to 10:90, more preferably in the range of 50:50 to 20:80, and most preferably in the range of 50:50 to 25:75. In the non-aqueous electrolytic solution system containing the vinylene carbonate compound and the alkyne compound, at least one aromatic compound preferably is a compound substituted with a fluorine atom. A fluorocyclohexylbenzene compound is particularly preferred.

The non-aqueous electrolytic solution according to the present invention can be used as a part of a secondary battery, particularly a lithium secondary battery. There is no specific limitation with respect to parts of the secondary battery other than the non-aqueous electrolytic solution. Conventional various parts can be used in the secondary battery.

Examples of the active cathode material include a complex metal oxide of lithium with cobalt, manganese or nickel. Only one material can be selected and used as the active cathode material. Further, two or more active cathode materials can be used in combination. Examples of the complex metal oxide include LiCoO₂, LiMn₂O₄, LiNiO₂, LiCo_(1-x)NixO₂ (0.01<x<1). Examples of the mixture include LiCoO₂ and LiMn₂O₄, LiCoO₂ and LiNiO₂, LiMn₂O₄ and LiNiO₂. The active cathode material preferably is a complex metal oxide of lithium, such as LiCoO₂, LiMn₂O₄, LiNiO₂. The material more preferably shows voltage of 4.3 V or more when the voltage of an open-circuit is measured using lithium as standard after complete the charge. The cathode material most preferably is a complex metal oxide of lithium containing Co or Ni. A part of a complex metal oxide of lithium can be replaced with another metal. For example, a part of Co contained in LiCoO₂ can be replaced with Sn, Mg, Fe, Ti, Al, Zr, Cr, V, Ga, Zn or Cu.

An electroconductive material that does not cause a chemical change can be used as the conductive material for the negative electrode. Examples of the conductive material include graphites such as natural graphite (e.g., scaly graphite), artificial graphite, and carbon blacks such as acetylene black, ketjenblack, channel black, furnace black, lamp black, thermal black. Graphite and carbon black can be used in combination at a certain mixing ratio. The cathode composite contains the conductive material preferably in an amount of 1 to 10 wt. %, and more preferably in an amount of 2 to 5 wt. %.

The positive electrode can be formed by mixing the active cathode material with the conductive material such as acetylene black, carbon black, and a binder to prepare a positive electrode composite material, pressing the positive electrode material on a collecting material, and heating them at a temperature of 50 to 250° C. for about 2 hours under reduced pressure. Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene/butadiene copolymer (SBR), acrylonitrile/butadiene copolymer (NBR), and carboxymethyl-cellulose (CMC). Examples of the collecting material include aluminum foil and a stainless lath board.

A material capable of absorbing and releasing lithium is used as the negative electrode. Examples of the material include metallic lithium, lithium alloy, a carbon material such as thermally decomposed carbon, coke, graphite (e.g., artificial graphite, natural graphite), a combustion product of an organic polymeric compound, or carbon fiber, tin, a tin compound, silicon, and a silicon compound.

The negative electrode (active anode material) preferably comprises a carbon material having a distance (d₀₀₂) between lattice faces (002) of 0.340 nm or less. The carbon material more preferably is graphite having a graphitic crystal structure with the distance (d₀₀₂) in the range of 0.335 to 0.340 nm. Only one material can be selected and used as the active anode material. Further, two or more active anode materials can be used in combination. A powdery material such as the carbon material can be used as a negative electrode composite material by mixing the material with a binder. Examples of the binder include ethylene/propylene diene interpolymer (EPDM), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene/butadiene copolymer (SBR), acrylonitrile/butadiene copolymer (NBR), and carboxymethylcellulose (CMC). There is no specification with respect to the method for forming the negative electrode. The anode can be prepared in the same manner as in the abovementioned method for forming the positive electrode.

There is no specific limitation with respect to the structure of the lithium secondary battery according to the present invention. Examples of the structure include a coin-shaped battery comprising a positive electrode, a negative electrode and a separator in the form of one or more layers, and a cylindrical or square-shaped battery comprising a positive electrode, a negative electrode and a separator in the form of a roll. A known separator such as a minute porous material, a fabric, and a nonwoven fabric can be used in the battery. The minute porous material can be made of polyolefin such as polypropylene, or polyethylene. The separator for the battery can be a single layer of a porous film. The separator can also comprise two or more porous films. The separator for the battery used in the present invention has gas permeability preferably in the range of 50 to 1,000 seconds per 100 cc, more preferably in the range of 100 to 800 seconds per 100 cc, and most preferably in the range of 300 to 500 seconds per 100 cc. In the case that the gas permeability is extremely high, the conductivity of lithium ion is lowered to cause insufficient function as battery separator. In the case that the gas permeability is extremely low, the mechanical strength is degraded. The void volume ratio is preferably in the range of 30 to 60%, more preferably in the range of 35 to 55%, and most preferably in the range of 40 to 50%. The void ratio is so adjusted to improve the battery capacity. The thickness of the separator for the battery is preferably thin to increase the energy density. On the other hand, the mechanical strength and the performance can also be considered about the thickness. The thickness of the separator is preferably in the range of 5 to 50 μm, more preferably in the range of 10 to 40 μm, and most preferably in the range of 15 to 25 μm.

The non-aqueous electrolytic solution according to the present invention is particularly effective in a lithium secondary battery in which a positive electrode and negative electrode composition layers are formed as high density layers. The positive electrode composition layer formed on aluminum foil has a density preferably in the range of 3.2 to 4.0 g/cm³, more preferably in the range of 3.3 to 3.9 g/cm³, and most preferably in the range of 3.4 to 3.8 g/cm³. If the density of the positive electrode is more than 4.0 g/cm³, it is substantially difficult to prepare the battery. The negative electrode composition layer formed on copper foil has a density preferably in the range of 1.3 to 2.0 g/cm³, more preferably in the range of 1.4 to 1.9 g/cm³, and most preferably in the range of 1.5 to 1.8 g/cm³. If the density of the negative electrode is more than 2.0 g/cm³, it is substantially difficult to prepare the battery.

The electrode layer of the positive electrode according to the present invention has a thickness (per one surface of the collector) preferably in the range of 30 to 120 μm, and more preferably in the range of 50 to 100 μm. The electrode layer of the negative electrode according to the present invention has a thickness (per one surface of the collector) preferably in the range of 1 to 100 μm, and more preferably in the range of 3 to 70 μm. If the thickness is smaller than the preferred range, the quantity of an active material in the electrode material layer is lowered to decrease the battery capacity. If the thickness is larger than the preferred range, the cycle characteristics or the rate characteristics are unfavorably degraded.

There is no specific limitation with respect to the structure of the lithium secondary battery. Examples of the structure include a coin-shaped battery, a cylindrical battery, a square-shaped battery and a laminated battery, each of which comprises a positive electrode, a negative electrode, a porous separating membrane and an electrolytic solution.

The lithium secondary battery according to the present invention shows excellent cycle characteristics for a long term even if the final recharging voltage is higher than 4.2 V. The battery further shows excellent cycle characteristics even if the final recharging voltage is higher than 4.3 V. The final discharging voltage can be 2.5 V or more, and further can be 2.8 V or more. There is no specific limitation with respect to the current. The battery is generally discharged with the constant current of 0.1 to 3 C. The lithium secondary battery according to the present invention can be charged and discharged at a temperature of higher than −40° C., and preferably at a temperature of higher than 0° C. The battery can also be charged and discharged at a temperature of lower than 100° C., and preferably at a temperature of lower than 80° C.

A safety valve can be attached to a sealing plate to prevent the inner pressure from increasing in the lithium secondary battery according to the present invention. A part of the battery such as a battery cell (can) or a gasket can be cut to prevent the pressure from increasing. At least one of various conventional safety attachments (for example overcurrent-preventing devices such as a fuse, a bimetal and a PTC element) is preferably attached to the battery.

Two or more lithium secondary batteries according to the present invention can be placed in a battery package while arranging the batteries in series or parallel. A safety circuit (which has functions of monitoring conditions such ass voltage, temperature and current in each of the battery or in the combined batteries, and breaking the current) can be attached to the battery package in addition to a safety attachment such as a PTC element, a thermal fuse, a fuse and a current breaker.

EXAMPLES

The present invention is described by referring to the following examples.

Example 1

(Preparation of Non-Aqueous Electrolytic Solution)

A non-aqueous solvent of EC:PC:MEC having a volume ratio of 30:5:65 was prepared. In the solvent, LiPF₆ was dissolved to prepare a 1 M solution of an electrolyte salt. To the non-aqueous electrolytic solution, 0.1 wt. % of 2-propynyl methyl carbonate (an alkyne compound represented by the formula (II), based on the non-aqueous electrolytic solution) was added. To the solution, 3 wt. % of vinylene carbonate (based on the non-aqueous electrolytic solution) was further added.

(Preparation of Lithium Secondary Battery and Measurement of Battery Performance)

With 94 wt. % of LiCoO₂ (active cathode material), 3 wt. % of acetylene black (conductive material) and polyvinylidene fluoride (binder) were mixed. To the mixture, 1-methyl-2-pyrrolidone (solvent) was added. A surface of aluminum foil was coated with the resulting solution. The mixture was dried, molded under pressure, and heated to form a positive electrode composition layer (cathode).

With 95 wt. % of artificial graphite (active anode material) having a graphitic crystalline structure with a distance (d₀₀₂) of 0.335 nm between the lattice between lattice faces (002), 5 wt. % of polyvinylidene fluoride (binder) was mixed. To the mixture, 1-methyl-2-pyrrolidone (solvent) was added. A surface of copper foil was coated with the resulting solution. The mixture was dried, molded under pressure and heated to form a negative electrode composition layer (anode).

The positive electrode, the negative electrode and a separator comprising a micro porous polyethylene film (thickness: 20 μm) were placed in a battery vessel. The non-aqueous electrolytic solution was poured into the battery. The air having the dew point of −60° C. was introduced into the battery, and the battery was sealed to prepare a cylindrical battery having the size of 18650 (diameter: 18 mm, height: 65 mm). A pressure-discharging opening and an inner current breaker (PTC element) were attached to the battery. The positive electrode composition layer has the density of 3.5 g/cm³, and the negative electrode composition layer has the density of 1.6 g/cm³. The positive electrode composition layer has the thickness of 70 μm (per one surface of the collector), and the negative electrode composition layer has the thickness of 60 μm (per one surface of the collector).

The 18650 battery was charged with the constant current of 2.2 A (1 C) at a high temperature (60° C.) to reach 4.2 V. The battery was further charged under the constant voltage for 3 hours in total to reach the final voltage of 4.2 V. The battery was discharged under the constant current of 2.2 A (1 C) to reach the final voltage of 3.0 V. The cycle of charge and discharge was repeated. The initial discharging capacity (mAh) was the substantially same as the result using 1M of LiPF₃-EC/PC/MEC (volume ratio: 30/5/65) containing no alkyne compound as the non-aqueous electrolytic solution (Comparison Example 1 described below). The battery performance was measured after 300 cycles. The remaining rate of the discharging capacity to the initial discharging capacity (100%) was 79.2%. The initial discharging capacity (relative value) and the remaining rate of the discharging capacity after 300 cycles are set forth in Table 1.

Examples 2-4

Cylindrical batteries having the size of 18650 were prepared in the same manner as in Example 1, except that non-aqueous electrolytic solutions were prepared using 0.5 wt. %, 1 wt. % and 5 wt. % of 2-propynyl methyl carbonate respectively as the additive. The cycle of charge and discharge was tested in the same manner as in Example 1. The initial discharging capacity (relative value) and the remaining rate of the discharging capacity after 300 cycles are set forth in Table 1.

Example 5

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 1, except that a non-aqueous electrolytic solution was prepared using 1 wt. % of 2-propynyl methyl carbonate and 0.1 wt. % of vinylene carbonate as the additives. The cycle of charge and discharge was tested in the same manner as in Example 1. The initial discharging capacity (relative value) and the remaining rate of the discharging capacity after 300 cycles are set forth in Table 1.

Example 6

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 1, except that a non-aqueous electrolytic solution was prepared using 1 wt. % of 2-propynyl methyl carbonate and 5 wt. % of vinylene carbonate as the additives. The cycle of charge and discharge was tested in the same manner as in Example 1. The initial discharging capacity (relative value) and the remaining rate of the discharging capacity after 300 cycles are set forth in Table 1.

Comparison Example 1

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 1, except that a non-aqueous electrolytic solution was prepared using no 2-propynyl methyl carbonate and 3 wt. % of vinylene carbonate as the additives. The cycle of charge and discharge was tested in the same manner as in Example 1. The initial discharging capacity (relative value) and the remaining rate of the discharging capacity after 300 cycles are set forth in Table 1.

Comparison Example 2

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 1, except that a non-aqueous electrolytic solution was prepared using 3 wt. % of 2-propynyl methyl carbonate and no vinylene carbonate as the additives. The cycle of charge and discharge was tested in the same manner as in Example 1. The initial discharging capacity (relative value) and the remaining rate of the discharging capacity after 300 cycles are set forth in Table 1. TABLE 1 Lithium 2-Propynyl Initial Remaining secondary Vinylene methyl discharging rate of battery carbonate carbonate capacity capacity Example 1 3 wt. % 0.1 wt. % 1.00 79.2% Example 2 3 wt. % 0.5 wt. % 1.00 82.1% Example 3 3 wt. % 1 wt. % 1.00 82.5% Example 4 3 wt. % 5 wt. % 1.00 81.1% Example 5 0.1 wt. % 1 wt. % 1.00 78.3% Example 6 5 wt. % 1 wt. % 1.00 80.1% Comp. Ex. 1 3 wt. % 0 wt. % 1.00 64.3% Comp. Ex. 2 0 wt. % 3 wt. % 1.00 65.8%

As is evident from the results shown in Table 1, a discharging capacity is kept with a high remaining rate. The excellent cycle characteristics are achieved by adding both of a vinylene carbonate compound and an alkyne compound to a non-aqueous electrolytic solution according to the present invention.

Example 7

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 1, except that a non-aqueous electrolytic solution was prepared using 1 wt. % of 2-propynyl methanesulfonate (a compound represented by the formula (II)) as the alkyne compound. The cycle of charge and discharge was tested in the same manner as in Example 1. The results are shown below.

Initial discharging capacity (relative value):

1.00

Remaining rate of discharging capacity after 300 cycles:

82.7

Example 8

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 1, except that a non-aqueous electrolytic solution was prepared using 1 wt. % of 2-butynylene bis(methyl carbonate) (a compound represented by the formula (III)) as the alkyne compound. The cycle of charge and discharge was tested in the same manner as in Example 1. The results are shown below.

Initial discharging capacity (relative value):

1.00

Remaining rate of discharging capacity after 300 cycles:

81.3

Example 9

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 1, except that a non-aqueous electrolytic solution was prepared using 1 wt. % of 2-butynylene bis(methanesulfonate) (a compound represented by the formula (III)) as the alkyne compound. The cycle of charge and discharge was tested in the same manner as in Example 1. The results are shown below.

Initial discharging capacity (relative value):

1.00

Remaining rate of discharging capacity after 300 cycles:

81.4

Example 10

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 1, except that a non-aqueous electrolytic solution was prepared using 1 wt. % of 2,4-hexadiynylene bis(methyl carbonate) (a compound represented by the formula (IV)) as the alkyne compound. The cycle of charge and discharge was tested in the same manner as in Example 1. The results are shown below.

Initial discharging capacity (relative value):

1.00

Remaining rate of discharging capacity after 300 cycles:

80.3

Example 11

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 1, except that a non-aqueous electrolytic solution was prepared using 0.5 wt. % of di(2-propynyl) carbonate (a compound represented by the formula (V)) as the alkyne compound. The cycle of charge and discharge was tested in the same manner as in Example 1. The results are shown below.

Initial discharging capacity (relative value):

1.00

Remaining rate of discharging capacity after 300 cycles:

80.5

Example 12

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 1, except that a non-aqueous electrolytic solution was prepared using 0.5 wt. % of di(2-propynyl) sulfite (a compound represented by the formula (VI)) as the alkyne compound. The cycle of charge and discharge was tested in the same manner as in Example 1. The results are shown below.

Initial discharging capacity (relative value):

1.00

Remaining rate of discharging capacity after 300 cycles:

82.5

Example 13

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 1, except that a non-aqueous electrolytic solution was prepared using 0.2 wt. % of di(2-propynyl) oxalate (a compound represented by the formula (VI)) as the alkyne compound. The cycle of charge and discharge was tested in the same manner as in Example 1. The results are shown below.

Initial discharging capacity (relative value):

1.00

Remaining rate of discharging capacity after 300 cycles:

81.7

Example 14

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 1, except that a non-aqueous electrolytic solution was prepared using 0.1 wt. % of phenylacetylene (a compound represented by the formula (VII)) as the alkyne compound. The cycle of charge and discharge was tested in the same manner as in Example 1. The results are shown below.

Initial discharging capacity (relative value):

1.00

Remaining rate of discharging capacity after 300 cycles:

80.4

Example 15

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 1, except that a non-aqueous electrolytic solution was prepared using 1 wt. % of 2-propynyl methanesulfonate (a compound represented by the formula (II)) as the alkyne compound, and LiMn₂O₄ was used as the positive electrode (active cathode material) in place of LiCoO₂. The cycle of charge and discharge was tested in the same manner as in Example 1. The results are shown below.

Initial discharging capacity (relative value):

0.87

Remaining rate of discharging capacity after 300 cycles:

80.8

Example 16

A non-aqueous solvent of EC:DMC:DEC having a volume ratio of 30:20:50 was prepared. In the solvent, LiPF₆ and LiN(SO₂CF₃)₂ were dissolved to prepare a solution of electrolyte salts having the concentrations of 0.9 M and 0.1 M respectively. To the non-aqueous electrolytic solution, 1 wt. % of 1,3-propanesultone (PS, based on the nonaqueous electrolytic solution) and 2 wt. % of cyclohexylbenzene (CHB, based on the non-aqueous electrolytic solution) were added. To the non-aqueous electrolytic solution, 1 wt. % of 2-propynyl methyl carbonate (an alkyne compound represented by the formula (II), based on the non-aqueous electrolytic solution) and 1 wt. % of vinylene carbonate (based on the non-aqueous electrolytic solution) were further added as the additives.

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 1, except that the above-prepared non-aqueous electrolytic solution was used. The cycle of charge and discharge was tested in the same manner as in Example 1. The results are shown below.

Initial discharging capacity (relative value):

1.00

Remaining rate of discharging capacity after 300 cycles:

82.2

Example 17

A non-aqueous solvent of EC:DMC:DEC having a volume ratio of 30:20:50 was prepared. In the solvent, LiPF₆ was dissolved to prepare a solution of an electrolyte salt having the concentration of 1 M. To the non-aqueous electrolytic solution, 0.5 wt. % of biphenyl (BP, based on the non-aqueous electrolytic solution) and 2 wt. % of cyclohexylbenzene (CHB, based on the non-aqueous electrolytic solution) were added. To the non-aqueous electrolytic solution, 0.5 wt. % of di(2-propynyl) sulfite (an alkyne compound represented by the formula (VI), based on the non-aqueous electrolytic solution) and 1 wt. % of vinylene carbonate (based on the non-aqueous electrolytic solution) were further added as the additives.

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 1, except that the above-prepared non-aqueous electrolytic solution was used. The cycle of charge and discharge was tested in the same manner as in Example 1. The results are shown below.

Initial discharging capacity (relative value):

1.00

Remaining rate of discharging capacity after 300 cycles:

81.1

Example 18

A non-aqueous solvent of EC:DMC:DEC having a volume ratio of 30:20:50 was prepared. In the solvent, LiPF₆ was dissolved to prepare a solution of an electrolyte salt having the concentration of 1 M. To the non-aqueous electrolytic solution, 1 wt. % of tert-butylbenzene (TBB, based on the non-aqueous electrolytic solution) and 1 wt. % of cyclohexylbenzene (CHB, based on the non-aqueous electrolytic solution) were added. To the non-aqueous electrolytic solution, 0.5 wt. % of di(2-propynyl) sulfite (an alkyne compound represented by the formula (VI), based on the non-aqueous electrolytic solution) and 1 wt. % of vinylene carbonate (based on the non-aqueous electrolytic solution) were further added as the additives.

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 1, except that the above-prepared non-aqueous electrolytic solution was used. The cycle of charge and discharge was tested in the same manner as in Example 1. The results are shown below.

Initial discharging capacity (relative value):

1.00

Remaining rate of discharging capacity after 300 cycles:

81.4

Example 19

A non-aqueous solvent of EC:DMC:DEC having a volume ratio of 30:20:50 was prepared. In the solvent, LiPF₆ was dissolved to prepare a solution of an electrolyte salt having the concentration of 1 M. To the non-aqueous electrolytic solution, 1 wt. % of tert-pentylbenzene (TPB, based on the non-aqueous electrolytic solution) and 1 wt. % of cyclohexylbenzene (CHB, based on the non-aqueous electrolytic solution) were added. To the non-aqueous electrolytic solution, 0.5 wt. % of di(2-propynyl) sulfite (an alkyne compound represented by the formula (VI), based on the non-aqueous electrolytic solution) and 1 wt. % of vinylene carbonate (based on the non-aqueous electrolytic solution) were further added as the additives.

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 1, except that the above-prepared non-aqueous electrolytic solution was used. The cycle of charge and discharge was tested in the same manner as in Example 1. The results are shown below.

Initial discharging capacity (relative value):

1.00

Remaining rate of discharging capacity after 300 cycles:

81.8

Example 20

(Preparation of Non-Aqueous Electrolytic Solution)

A non-aqueous solvent of EC:MEC having a volume ratio of 30:70 was prepared. In the solvent, LiPF₆ was dissolved to prepare a 1 M solution of an electrolyte salt. To the non-aqueous electrolytic solution, 0.3 wt. % of di(2-propynyl) oxalate (an alkyne compound represented by the formula (VI), based on the non-aqueous electrolytic solution) was added. To the solution, 2 wt. % of vinylene carbonate (based on the non-aqueous electrolytic solution) was further added. To the solution, 1 wt. % of cyclohexylbenzene (CHB, based on the non-aqueous electrolytic solution) and 3 wt. % of 1-fluoro-4-cyclohexylbenzene (FCHB, based on the non-aqueous electrolytic solution) were furthermore added.

(Preparation of Lithium Secondary Battery and Measurement of Battery Performance)

With 94 wt. % of LiCoO₂ (active cathode material), 3 wt. % of graphite (conductive material) and polyvinylidene fluoride (binder) were mixed. To the mixture, 1-methyl-2-pyrrolidone (solvent) was added. A surface of aluminum foil was coated with the resulting solution. The mixture was dried, molded under pressure, and heated to form a positive electrode composition layer (cathode).

With 95 wt. % of artificial graphite (active anode material) having a graphitic crystalline structure with a distance (d₀₀₂) of 0.335 nm between the lattice between lattice faces (002), 5 wt. % of polyvinylidene fluoride (binder) was mixed. To the mixture, 1-methyl-2-pyrrolidone (solvent) was added. A surface of copper foil was coated with the resulting solution. The mixture was dried, molded under pressure and heated to form a negative electrode composition layer (anode).

The positive electrode, the negative electrode and a separator comprising a micro porous polyethylene film (thickness: 20 μm) were placed in a battery vessel. The non-aqueous electrolytic solution was poured into the battery. Carbon dioxide having the dew point of −60° C. was introduced into the battery, and the battery was sealed to prepare a cylindrical battery having the size of 18650 (diameter: 18 mm, height: 65 mm). A pressured-discharging opening and an inner current breaker (PTC element) were attached to the battery. The positive electrode composition layer has the density of 3.5 g/cm³, and the negative electrode composition layer has the density of 1.6 g/cm³. The positive electrode composition layer has the thickness of 70 μm (per one surface of the collector), and the negative electrode composition layer has the thickness of 60 μm (per one surface of the collector).

The 18650 battery was charged with the constant current of 2.2 A (1 C) at a high temperature (60° C.) to reach 4.2 V. The battery was further charged under the constant voltage for 3 hours in total to reach the final voltage of 4.2 V. The battery was discharged under the constant current of 2.2 A (1 C) to reach the final voltage of 3.0 V. The cycle of charge and discharge was repeated. The initial discharging capacity (mAh) was the substantially same (1.01) as the result using 1M of LiPF₆-EC/PC/MEC (volume ratio: 30/5/65) containing no alkyne compound as the non-aqueous electrolytic solution (Comparison Example 1 described above). The battery performance was measured after 300 cycles. The remaining rate of the discharging capacity to the initial discharging capacity (100%) was 82.5%.

After the cycle test was repeated five times, the 18650 battery was fully charged to reach 4.2V at the ordinary temperature (20° C.), and further charged with the constant current of 2.2 A (1 C) for 2 hours to conduct an excessive charge test. The temperature on the surface of the battery was lower than 120° C., which is the standard highest temperature for safety.

Example 21

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 20, except that a non-aqueous electrolytic solution was prepared using 4 wt. % of fluorobenzene (FB) in place of 1-fluoro-4-cyclohexylbenzene (FCHB) as the additive. The cycle test of charge and discharge and the excessive charge test were conducted in the same manner as in Example 20. The results are shown below.

Initial discharging capacity (relative value):

1.01

Remaining rate of discharging capacity after 300 cycles:

82.1

Surface temperature of battery in excessive charge test:

lower than 120° C.

Example 22

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 20, except that a non-aqueous electrolytic solution was prepared using 1 wt. % of 1-fluoro-4-cyclohexylbenzene (FCHB) and 4 wt. % of fluorobenzene (FB) in place of cyclohexylbenzene (CHB) as the additives. The cycle test of charge and discharge and the excessive charge test were conducted in the same manner as in Example 20. The results are shown below.

Initial discharging capacity (relative value):

1.01

Remaining rate of discharging capacity after 300 cycles:

82.2

Surface temperature of battery in excessive charge test:

lower than 120° C.

Example 23

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 20, except that a non-aqueous electrolytic solution was prepared using 1.5 wt. % of cyclohexylbenzene (CHB) and 1 wt. % of 2,4-difluoroanisole (DFA) in place of 1-fluoro-4-cyclohexylbenzene (FCHB) as the additives. The cycle test of charge and discharge and the excessive charge test were conducted in the same manner as in Example 20. The results are shown below.

Initial discharging capacity (relative value):

1.01

Remaining rate of discharging capacity after 300 cycles:

81.5

Surface temperature of battery in excessive charge test:

lower than 120° C.

Example 24

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 20, except that a non-aqueous electrolytic solution was prepared using 2 wt. % of 1-fluoro-4-cyclohexylbenzene (FCHB) and 1 wt. % of 2,4-difluoroanisole (DFA) in place of cyclohexylbenzene (CHB) as the additives. The cycle test of charge and discharge and the excessive charge test were conducted in the same manner as in Example 20. The results are shown below.

Initial discharging capacity (relative value):

1.01

Remaining rate of discharging capacity after 300 cycles:

81.9

Surface temperature of battery in excessive charge test:

lower than 120° C.

Example 25

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 20, except that a non-aqueous electrolytic solution was prepared using 0.4 wt. % of ethylene sulfite (ES) in addition to di(2-propynyl) oxalate (an alkyne compound represented by the formula (VI)), vinylene carbonate (VC), cyclohexylbenzene (CHB) and 1-fluoro-4-cyclohexylbenzene (FCHB) as the additives. The cycle test of charge and discharge and the excessive charge test were conducted in the same manner as in Example 20. The results are shown below.

Initial discharging capacity (relative value):

1.01

Remaining rate of discharging capacity after 300 cycles:

82.6

Surface temperature of battery in excessive charge test:

lower than 120° C.

Example 26

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 20, except that a non-aqueous electrolytic solution was prepared using 0.3 wt. % of di(2-propynyl) oxalate, 0.3 wt. % of di(2-propynyl) sulfite, 2 wt. % of vinylene carbonate (VC), 1 wt. % of tert-pentylbenzene (TPB) and 3 wt. % of 1-fluoro-4-cyclohexylbenzene (FCHB) as the additives. The cycle test of charge and discharge and the excessive charge test were conducted in the same manner as in Example 20. The results are shown below.

Initial discharging capacity (relative value):

1.01

Remaining rate of discharging capacity after 300 cycles:

83.2

Surface temperature of battery in excessive charge test:

lower than 120° C.

Example 27

A non-aqueous solvent of EC:PC:DMC:DEC having a volume ratio of 30:5:15:50 was prepared. In the solvent, LiPF₆ was dissolved to prepare a 1 M solution of an electrolyte salt. To the non-aqueous electrolytic solution, 0.5 wt. % of 2-propynyl formate (an alkyne compound represented by the formula (II), based on the non-aqueous electrolytic solution) and 2 wt. % of vinylene carbonate (based-on the non-aqueous electrolytic solution) was added.

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 20, except that the non-aqueous electrolytic solution was used. The cycle test of charge and discharge and the excessive charge test were conducted in the same manner as in Example 20. The results are shown below.

Initial discharging capacity (relative value):

1.00

Remaining rate of discharging capacity after 300 cycles:

82.4

Surface temperature of battery in excessive charge test:

lower than 120° C.

Example 28

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 27, except that a non-aqueous electrolytic solution was prepared using 0.5 wt. % of 2-butynylene diformate (a compound represented by the formula (III)). The cycle test of charge and discharge and the excessive charge test were conducted in the same manner as in Example 20. The results are shown below.

Initial discharging capacity (relative value):

1.00

Remaining rate of discharging capacity after 300 cycles:

82.0

Surface temperature of battery in excessive charge test:

lower than 120° C.

Example 29

A cylindrical battery having the size of 18650 was prepared in the same manner as in Example 27, except that a non-aqueous electrolytic solution was prepared using 0.5 wt. % of 2,4-hexadiynylene diformate (a compound represented by the formula (IV)). The cycle test of charge and discharge and the excessive charge test were conducted in the same manner as in Example 20. The results are shown below.

Initial discharging capacity (relative value):

1.00

Remaining rate of discharging capacity after 300 cycles:

81.4

Surface temperature of battery in excessive charge test:

lower than 120° C. 

1. A non-aqueous electrolytic solution comprising an electrolyte salt in a nonaqueous solvent for a lithium secondary battery, wherein the non-aqueous electrolytic solution further contains a vinylene carbonate compound represented by the formula (I) in an amount of 0.01 to 10 wt. %, and at least one alkyne compound represented by the formula (II), (III), (IV), (V) in an amount of 0.01 to 10 wt. %:

in which each of R¹ and R² independently is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;

in which each of R³ to R⁵ independently is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, or R⁴ and R⁵ are combined with each other to form a cycloalkylene group having 3 to 6 carbon atoms; x is 1 or 2; and Y¹ or an aryl group having 6 to 12 carbon atoms, or R¹⁰ and R¹¹ or R¹² and R¹³ are combined with each other to form a cycloalkylene group having 3 to 6 carbon atoms; x is 1 or 2; Y⁴ is —COOR²³, —COR²³, or —SO₂R²³, wherein R²³ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms; and Y⁵ is —COOR²⁴, —COR²⁴, or —SO₂R²⁴, wherein R²⁴ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms;

in which each of R¹⁴ to R¹⁹ independently is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, or R¹⁵ and R¹⁶ or R¹⁷ and R¹⁸ are combined with each other to form a cycloalkylene group having 3 to 6 carbon atoms; and x is 1 or 2;

in which each of R²⁵ to R²⁷ independently is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, or R²⁶ and R²⁷ are combined with each other to form a cycloalkylene group having 3 to 6 carbon atoms; x is 1 or 2; W is sulfinyl, sulfonyl, or oxalyl; and Y⁶ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.
 2. The non-aqueous electrolytic solution of claim 1, wherein the non-aqueous electrolytic solution contains the vinylene carbonate compound in an amount of 0.05 to 5 wt. %.
 3. The non-aqueous electrolytic solution of claim 1, wherein the non-aqueous electrolytic solution contains the vinylene carbonate compound in an amount of 0.1 to 3 wt. %.
 4. The non-aqueous electrolytic solution of claim 1, wherein the non-aqueous electrolytic solution contains the alkyne compound in an amount of 0.05 to 5 wt. %.
 5. The non-aqueous electrolytic solution of claim 1, wherein the non-aqueous electrolytic solution contains the alkyne compound in an amount of 0.1 to 3 wt. %.
 6. The non-aqueous electrolytic solution of claim 1, wherein the vinylene carbonate compound is vinylene carbonate.
 7. The non-aqueous electrolytic solution of claim 1, wherein the alkyne compound is 2-propynyl methyl carbonate, 2-propynyl methanesulfonate, 2-butynylene bis(methyl carbonate), 2-butynylene bis(methanesulfonate), 2,4-hexadiynylene bis(methyl carbonate), di(2-propynyl) carbonate, di(2-propynyl) sulfite, di(2-propynyl) oxalate, ethyl 2-propynyl oxalate, 2-propynyl formate, 2-butynylene diformate or 2,4-hexadiynylene diformate.
 8. The non-aqueous electrolytic solution of claim 1, wherein the non-aqueous electrolytic solution further contains an aromatic compound in an amount of 0.1 to 5 wt. %, said aromatic compound being selected from the group consisting of cyclohexylbenzene, a fluorocyclohexylbenzene compound, biphenyl, terphenyl, diphenyl ether, 2-fluorophenyl phenyl ether, 4-fluorophenyl phenyl ether, fluorobenzene, difluorobenzene, 2-fluorobiphenyl, 4-fluorobiphenyl, 2,4-difluoroanisole, tertbutylbenzene, 1,3-di-tert-butylbenzene, 1-fluoro-4-pentylbenzene, tert-butyl biphenyl, tert-pentyl biphenyl, a partially hydrogenated o-terphenyl, a partially hydrogenated m-terphenyl and a partially hydrogenated p-terphenyl.
 9. The non-aqueous electrolytic solution of claim 1, wherein the non-aqueous electrolytic solution further contains a mixture having a weight ratio of 50:50 to 10:90 in a total amount of 0.1 to 5 wt. %, said mixture being selected from the group consisting of a mixture of biphenyl and cyclohexylbenzene, a mixture of cyclohexylbenzene and tert-butylbenzene, a mixture of cyclohexylbenzene and tert-pentylbenzene, a mixture of biphenyl and fluorobenzene, a mixture of cyclohexylbenzene and fluorobenzene, a mixture of 2,4-difluoroanisole and cyclohexylbenzene, a mixture of cyclohexylbenzene and 1-fluoro-4-tert-butylbenzene, a mixture of cyclohexylbenzene and a fluorocyclohexylbenzene compound, a mixture of a fluorocyclohexylbenzene compound and fluorobenzene, and a mixture of 2,4-difluoroanisole and a fluorocyclohexylbenzene compound.
 10. A lithium secondary battery comprising a positive electrode, a negative electrode and a non-aqueous electrolytic solution, wherein the positive electrode comprises lithium mixed oxide, wherein the negative electrode comprises a material capable of absorbing and releasing lithium, and wherein the non-aqueous electrolytic solution is the solution defined in claim
 1. 11. A lithium secondary battery comprising a positive electrode, a negative electrode and a non-aqueous electrolytic solution, wherein the positive electrode composition layer having a density in the range of 3.2 to 4.0 g/cm³ provided on aluminum foil, said positive electrode layer composition layer comprising lithium mixed oxide, and wherein the non-aqueous electrolytic solution is the solution defined in claim
 1. 12. A lithium secondary battery comprising a positive electrode, a negative electrode and a non-aqueous electrolytic solution, wherein the negative electrode comprises a negative electrode composition layer having a density in the range of 1.3 to 2.0 g/cm³ provided on copper foil, said negative electrode layer composition layer comprising a material capable of absorbing and releasing lithium, and wherein the non-aqueous electrolytic solution is the solution defined in claim
 1. 13. A lithium secondary battery comprising a positive electrode, a negative electrode and a non-aqueous electrolytic solution, wherein the positive electrode comprises a positive electrode composition layer having a density in the range of 3.2 to 4.0 g/cm³ provided on aluminum foil, said positive electrode layer composition layer comprising lithium mixed oxide, wherein the negative electrode comprises a negative electrode composition layer having a density in the range of 1.3 to 2.0 g/cm³ provided on copper foil, said negative electrode layer composition layer comprising a material capable of absorbing and releasing lithium, and wherein the non-aqueous electrolytic solution is the solution defined in claim
 1. 